Insecticidal and acaricidal 2-phenyl-benzimidazoles

ABSTRACT

New 2-phenyl-benzimidazoles which are substituted by at least three halogen and/or trifluoromethyl radicals none of which, however, is present at the phenyl radical in an orthoposition relative to the link to the benzimidazole moiety, and optionally by further substituents; as well as their alkali metal and alkaline earth metal salts; which compounds are useful as insecticides and acaricides; and insecticidal and acaricidal compositions containing such compounds as active ingredients; a method of controlling insects and acarinae, and of protecting keratinous material from damage by insects or their larvae, with the aid of such novel compounds; as well as keratinous materials protected with the aid of the said compounds.

United States Patent Wilhelm E. Frick Baselland;

Horst llarle, Allschwil; Thomas Wenger, Riehen; Anton Weiss, Basel, all of [72] inventors Switzerland [2|] Appl. No. 634,092

[22] Filed Apr. 27,1967

[45] Patented Nov. 30, 1971 [73 Assignee Geigy Chemical Corporation Ardsley, N.Y.

[32] Priority May 6, 1966 [3 3 Switzerland [54] INSECTICIDAL AND ACARlClDAL Z-PHENYL- Dandegaonker et al. Monatsh. Chem. Vol. 96, No. 2, pages 6l4- 624 1965) O l.M73

' Primary Examiner-Natalie Trousof Allorneys- Karl F, .lorda and Martin J. Spellman ABSTRACT: New Z-phenyl-benzimidazoles which are substituted by at least three halogen and/or trifluoromethyl radicals none of which. however, is present at the phenyl radical in an orthoposition relative to the link to the benzimidazole moiety, and..optionally by further substituents; as well as their alkali metaland alkaline earth metal salts; which compounds are useful as insecticides and acaricides; and insecticidal and acaricidal compositions containing such compounds as active ingredients; a method of controlling insects and acarinae, and of protecting keratinous material from damage by insects or their larvae, with the aid of such novel compounds; as well as keratinous materials protected with the aid of the said compounds.

INSECTICIDAL AND ACARICIDAL Z-PIIENYL- BENZIMIDAZOLES BACKGROUND OF THE INVENTION 1 Field of the Invention The present invention concerns new substituted benzimidazole derivatives having insecticidal properties as well as insecticidal and acaricidal agents which contain these new benzimidazole derivatives as active substances and, in particular, serve to combat keratin-eating insects and their larvae, as well as the use of these active substances and the agents containing them for combating insects and spiders, in particular however, for the protection of keratinuous materials from attackby such insects.

2. Description of the Prior Art Of the benzimidazole derivatives known today, those containing a low-molecular halogenoalkyl radical in the 2-position have been suggested as herbicidal and pesticidal active substances for combatting weeds, insects, nematodes ad mites (Dutch application open to public inspection 64/l04l3; Angew. Chem. 77 I965), pages 8 l4 and 91 1-912. These literature citations make no mention of a keratin-protecting action of these substances. These 2 halogen-alkyl-benzimidazoles, if they are polyhalogenated in the nucleus, have marked toxicity to warmblooded animals which limits their possibilities of application.

DESCRIPTION OF THE INVENTION It has now been found that new substituted 2-phenylbenzimidazoles of the formula wherein R represents hydrogen or a metal cation, each of the symbols X and X, represents a halogen atom having an atomic number of at most 35, a trifluoromethyl group, an alkyl or alkoxy radical, the nitro, hydroxyl or amino group, an alkanoylamino group, a substituted or unsubstituted phenoxy or phenylsulphonyl group or the radical of sulfonic acid and its amide and ester forms,

n represents a whole number from one to four, and

m represents a whole number from one to five, with the condition that, in all, at least three of the substituents symbolized by X and X, are halogen atoms and/or trifluoromethyl radicals of which, however, none is in 2-or o-position at the phenyl radical B, and that there are, at most, two trifluoromethyl groups in each of the two-benzene nuclei of the molecule,

have excellent insecticidal and acaricidal properties, in particular, a marked action against keratinous material-devouring insects and their stages of development, e.g., the larvae of moths and other small butterflies, also fur ad carpet beetle larvae. For this reason the new active substances of formula I are particularly suitable for the protection of keratinous material such as wool and articles containing wool, from attack by such pests.

The strength of action of the new benzimidazole derivatives of formula 1 depends substantially on the nature of their substitution, by halogen atoms and/or trifluoromethyl groups; at least three such substituents must be present in the molecule in order to attain a satisfactory insecticidal action. Compared with known halogenated and/or trifluoromethylated 2- trifluoromethylbenzimidazoles which have been suggested as pesticidally active substances (Angew. Chem. 77 (l965) pages 814 and 91 1-912), the new compounds, while having about the same number of halogen substituents in the condensed benzene ring A, have much less toxicity to warmblooded animals. For example, the DL;,, of the known 4,5,6,7- tetrachloro-Z-trifluoromethylbenzimidazole to rats per os is less than 10 mgJkg. whereas OL of the 4,5,6,7-tetrachloro-2- (3,4-dichlorophenyl)benzimidazole according to the invention is higher than 5,000 mg./kg.

Compounds of formula I, v

wherein R is hydrogen, are acids which are capable of forming slats, e.g., with alkali metal hydroxides and alkaline earth metal hydroxides and the corresponding carbonates, in which salts R is the monovalent equivalent of a metal cation. Preferred salts are the soluble alkali metal salts, particularly the sodium and potassium salts.

All substituents X and X, can be the same or different but at least three of them must be halogen atoms of an atomic number of at most 35 and/or trifluoromethyl. The preferred halogen substituents are chlorine and bromine. Halogen substituents can be replaced by trifluoromethyl groups, but in practice it is not possible to build in more than two trifluoromethyl groups in each of the two benzene nuclei A and B of the molecule defined by formula I. In the phenyl radical B, no halogen atom or CF; group may be in orthoposition to the linking position to the benzimidazole structure as otherwise effective insecticidal activity is lost. The other radicals represented by X, may also be in 2 Z-and/or o-position at ring B. The benzene nuclei A and B have preferably not more than one of the other substituents, of which the alkyl, alkoxy and alkanoylamino radicals falling under the definition of X and X, have from one to five carbon atoms in their alkyl moiety; the methyl, methoxy and acetylamino radicals being preferred. Suitable substituted phenoxy and phenylsulphonyl radicals are those which are substituted by at least one halogen atom and/or one CF, group.

Among the compounds of formula I are those having the wherein R is hydrogen or an alkali or alkaline earth metal cation,

X is fluorine, chlorine, bromine, trifluoromethyl, alkanoylamino of from one to five carbon atoms or chlorophenylsulphonyl,

two of X, are hydrogen, chlorine, bromine, trifluoromethyl, nitro, chlorophenoxy, alkyl of from one to five carbon atoms or alkoxy of from one to five carbon atoms and the other X, is chlorine, bromine, trifluoromethyl, nitro, chlorophenoxy, alkyl of from one to five carbon atoms or alkoxy of from one to five carbon atoms, and

n is an integer of from one to four, with the condition that at least three of the substituents symbolized by X and X, are either halogen atoms or trifluoromethyl groups and that X and X, each may not represent more than two trifluoromethyl groups.

The new active substances have excellent affinity to keratinous fibers. Due to their affinity to such fibers, the 2- phenyl-benzimidazole derivatives of formula I draw from aqueous dispersions, and also from aqueous solutions of their salts, onto these fibers and in this way protect keratinous material treated therewith from injury caused by larvae from moths and other small butterflies as well as from injury caused by the larvae of the fur and carpet beeties (Anthrenus and Attagenus).

The compounds of formula I are also active, however, against other insects, including termites, and also mites, etc., and can thus be used generally in plant protection, particularly for industrial application in plant protection and protection of materials, e.g., for the protection of organic materials such as paper, wood, textiles, plastics, etc. from attack by insects and mites.

The new benzimidazole derivatives for formula I can be produced by the following methods:

a. o-Phenylenediamines, optionally substituted by radicals X of the formula are condensed e.g., in the melt, optionally in the presence of catalysts such as mineral acids, polyphosphoric acid or metaphosphoric acid esters, with optionally substituted benzoic acids or with their esters, amides, acid halides and nitriles, and optionally, subsequently chlorinated or brominated in at least one benzene nucleus, preferably in dimethyl forrnamide as solvent.

The new 2-phenyl-benzimidazoles are also obtained by a variation of this process when the o-phenylenediamines mentioned above are reacted with the corresponding benzaldehydes in the presence of an oxidizing agent such as copper acetate or nitrobenzene instead of with benzoic acid derivatives.

b. The new 2-phenyl-benzimidazoles can also be obtained by reductive cyclization, e.g., with zinc and hydrochloric acid, of correspondingly substituted N-benzoyl-- nitranilines. This cyclization can also be performed in steps. This method is of particular interest if the usual cyclization methods are made difiicult due to the presence of a sterically hindered specific substituent X. Starting from o-chloronitrobenzenes, first o-nitranilines are produced and then acylated in the amino group with a reactive benzoic acid derivative and in this way the N- benzoyl-o-nitranilines are obtained as starting materials for the reductive cyclization. The cyclized 2-phenylbenzimidazoles can then be halogenated in the benzene nuclei.

c. Finally, the new active substances of general formula I can also be obtained by oxidative cyclization of optionally substituted N-phenyl-benzamidines of the formula Preferably a hypochlorite is used as oxidizing agent. In this method it is better to sue unhalogenated or only slightly halogenated benzamidines as starting materials and, after cyclization, to halogenate the products obtained.

The latter method of oxidative cyclization of N-phenylbenzamidines is of particular interest if the nitranilines and l,2-phenylenediamines necessary for the production methods described above are difficulty accessible.

Elementary chlorine and bromine in particular are used for the halogenation of the 2-phenyl-benzimidazoles in order to introduce halogen or to increase the halogen substitution.

Water, aromatic hydrocarbons, halogenated hydrocarbons, N-alkylated acid amides and alcohols, e.g., methanol or glycol monomethyl ether can be used as solvents or diluents for the halogenation. The halogenation is preformed in aqueous medium with elementary chlorine or with nascent chlorine from hydrogen chloride in the presence of oxidizing agents, or with elementary bromine and bromate in the presence of dilute acid. Sulphuryl chloride is the principle example of an agent which gives off nascent chlorine.

Halogenation of the benzimidazoles with elementary chlorine or bromine in an N-alkylated organic acid amide, particularly dimethyl formamide, optionally in the presence .of

a catalyst, at temperatures between 0 and l00 C., is preferred.

The following examples describe the production of the new active substances of general formula I. Where not otherwise stated, parts and percentages are given by weight and the temperatures are given in degrees Centigrade.

EXAMPLE 1 2-( 3 ,5 -bis-trifluoromethyl-phenyl )-4,5,6,7-tetrachlorobenzimidazole a. 16.2 parts of 1,2-phenylenediamine are dissolved in parts of metaphosphoric acid triethyl ester while stirring and heating to 100. 26 parts of 3,5-bis-trifiuor0methyl benzoic acid are then added and the mixture is heated for 1 hour at After cooling to 50, l,500 parts of water are added and the suspension so formed is made weakly alkaline (pH=8) by the addition of solid sodium bicarbonate. The product is filtered, washed, dried and dissolved in ethanol. The side product, the diamide of o-phenylenediamine, which in practice is insoluble in ethanol, is removed and the 2-(3,5'-bistrifluoromethyl-phenyl)-benzimidazole is crystallized from aqueous alcohol: m.p. 2 l 8-2 l 9.

b. 18 parts of chlorine are introduced over a period of 2 hours into a 60 hot solution of 6.6 parts of 2-(3',5'-bistrifluoromethyl-phenyl)-benzimidazole and 0.1 parts of ironlll chloride in 100 parts by volume of dimethyl formamide. The reaction mixture is then added to 2,000 parts by volume of water while stirring vigorously. The precipitate formed is filtered off, washed with water and then dried. The 2-(3,5'- bis-trifluoromethyl-phenyl-4,5,6,7-tetrachloro-benzimidatole melts at 278.5-279.

EXAMPLE 2 2-(3',4'-dichlorophenyl)-4,7-dibromo-5,6-dichlorobenzimidazole a. A finely pulverized mixture of 18.7 parts of 4,5-dichloroortho-phenylenediamine and 19.] parts of 3,4-dichlorobenzoic acid is heated for 1 hour at l20-l 30 with I20 parts of metaphosphoric acid ethyl ester, while stirring. 2,000 parts of water are added to the cold reaction product and the suspension so obtained is made alkaline with solid sodium bicarbonate. The product is filtered off, dried and recystallized from ethanol.

The 2-(3',4'-dichlorophenyl)-5,6-dichlow-benzimidazole obtained melts at 25 l252.

b. l0 parts of 2-(3,4'-dichlorophenyl)-5,6-dichlorobenzimidazole are suspended in 200 parts of water and 3 parts of concentrated sulfuric acid are added. The whole is brought to the boil and simultaneously 8 parts of bromine and also a solution of 4.2 parts of potassium bromate in 60 parts of water are added dropwise within about I hour. The whole is then refluxed for 10 hours, again the amounts of bromine an bromate solution given above are added dropwise and the whole is refluxed for another 10 hours. Excess bromine is then distilled off and the reaction product, when cold, is filtered off under suction. The crude product is dissolved in a mixture of 2N sodium hydroxide solution and ethanol, the filtrate is acidified with dilute hydrochloric acid and the precipitate is filtered off, dried and recrystallized from ethanol. The 2-(3',4 '-dichlorophenyl)-4,7-dibromo-5,6-dichloro-benzimidatole melts at 269-270.

EXAMPLE 3 2-(3,4',5'-trichlorophenyl)-4,-bis-trifluoromethylbenzimidazole a. A mixture of 6.9 of 3,5-bis-trifluoromethyl aniline, 6.2 parts of 3,4,S-trichlorobenzonitrile and 4.2 parts of anhydrous zinc chloride is heated for 3 hours at 180. The cold melt is dissolved with warm alcohol, water and chloroform are added, the chloroform phase is removed, dried with MgSO, the chloroform is evaporated in-vacuo and the residue is recrystallized from hexane.

The N-( 3 ,5 -bis-trifluoromethyl-phenyl )-3 ,4'-5 trichlorobenzamidine so obtained crystallizes into needles which melt at l48-l 5 1.

b. 17.4 parts of this benzamidine are dissolved in 150 parts by volume of methanol and 80 parts by volume of 1N HCL are added. 28 parts by volume of L5 molar NaOCL solution are then added dropwise at room temperature and the whole is stirred for l minutes. The reaction milieu is made alkaline by the addition of 7.5 parts of sodium carbonate and then the whole is refluxed for 30 minutes. After evaporation of the methanol, the reaction product is isolated and recrystallized from methanol. The 2-(3',4,5'-trichlorophenyl)-4,6bistrifluoromethyl-benzimidazole is obtained in this way as silky needles which melt at l88-l 90.

EXAMPLE 4 2-(3',4'-dichlorophenyl)-4,5,6,7-tetrachloro-benzimidazole A mixture of 12.3 parts of tetrachloro-o-phenylenediamine, 105 parts of 3,4-dichlorobenzoyl chloride an 50 parts by volume of 25 percent hydrochloric acid is heated in a bomb tube for 40 minutes at l80-l85. After cooling, dilute sodium hydroxide solution and alcohol are added to the reaction mixture and the alkaline solution of the reaction product is treated with animal charcoal and filtered. Dilute hydrochloric acid is added to the filtrate and the precipitate formed is filtered off under suction and washed with water. After recrystallization from alcohol, the end product melts at 277-278.

The following benzimidazole derivatives of general formula I are produced in a manner analogous to those described in the above examples:

TABLE I No. Compound M.P.,

5 2-3-chloropheny1)4,5,6,7-tetrach1orobenzimidazole- 322-324 6 2- 4-ohlorophenyl)-4,5,6,7-tetrachlore-benzimidazole. 265-270 7 2-(3-bromophenyl)-4,5,6,7-tatrachloro-benz1m1dazole 327-330 8 2-(3-chlorophenyl)-4,5,6,7-tetrabromo-benzimidazole 320-322 9 2-(4-ch1orophenyl)4,6,6,7-tetrabromo-benzlmidazole 277-279 10 2-(3-bromophenyl)-4,5,6,7-tetrabromo-benzlmidazole-. 325-328 11 2-(4'-bromopheny1)-4,6,6,7-tetrabroIno-benzimldazole. 253- 66 12 2-(3'-trlfluotomethyl-phenyl)4,6,6,7-tetraehloro 321-323 benzimidazole.

13 2-(4-tl'lfluoromethyl-phenyl)-4,5,6,7-tetraehloro- 274-276 benzimidazole.

2-(4'-nltrophenyl) 4,6,6,7-tetrachloro-benzimtdazole 317-319 15 2-I4-(p-chlorophenoxy)-phenyl]-4,6,6,7-tetrachloro- 246-248 benzimidazole.

1e 2-(3'l,5-din1tropheny1)4,5,6,7-tetrachloro-benzim1da- 362-864 zo e.

17 2-(3,4'-dlmethyl-pheny1)4,5,6,7-tetrachloro-benz1mid- 290-293 an e.

18 2-(3,4l-dlchloropheny1)-4,5,6,7-tetrabromo-benzlmld- 282-283 19 2-(3,5-bls-trlfluoromethyl-phenyl)-4,5,0,7-tetra- 285-286 Monro-benzimidazole.

20 2(3,4,5-trlchl0rophenyl)-4,5,6,7-tetrachloro- 297-300 benzimidazole.

21 2-(3,4,6-trlmethoxy-phenyl)-4,5,6,7-tetrachloro- 310-311 benzimidazole.

22 2-(4'- ihlorophenyl)4,6,6-trlchloro-7-bromo-beuzimtd- 258-269 am e.

23 2-(3',4-dlchlot0pheny1)-4,5,6-tr1ch1or0-7-br0mo- 274-276 benzimidazole.

24 2-(2-hydroxy-3,5-d1chlorophenyl)4,5,7-trichloro- 262-264 benzimidazole.

25 2-(3,4-d1chlorophenyl)-6-bromo-4,5,7-trichloro- 270-273 benzimidazole.

26 2-3,4-dlehlorophenyl)-4,6,7-trloblate-benzimidazole 292-293 27 2- 3-trlfluoromethyl-4-chlorophenyl)-4,6,7-tricholro- 262-264 benzimidazole.

28 2-(34i-dlchlorophenyl)-4.6,7-tricbloro-5-fluorobenzlm1d- 268-270 am e.

29 .1 2-(3,4-dlchlorophenyl)4,6,7-trichlordfi-aeetylamino- 230-250 benzimidazole.

30 2-(3,5'-b1s-trifluoromethyl-phenyl)-4,6.7,trlbromo-5- 243-246 trlfiuoromethylbenzlmidazole.

31 2-(3,4-dlchl0rophenyl)-4,6-dichloro-7-(pcblorophenyl- 302-304 sulphonyD-benzlmldazole.

32 2-(3',4'-dlchlorophenyl)-4,6-dlbrom0-7-chl0ro-5-tri- 214-215 fiuoromethyl-benzimidazole.

33 2-(3,4'-d1chlorophenyl)-4,7-dlbromo-5,6-dichloro- 268-270 benzimidazole.

34 Z-(3,4-dlch1orophenyl)-5,6-(llchloro-benzimldazole. 251-252 35 2-(3',4'-dleh1oro-2'-Sulphonyl-phenyl)-5,6-dlchl0ro- 360 benzimidazole.

36 2-(3,5'-bls-trlfiuoromethyl-phenyD-5-trifluoromethyl- 212-215 4,6-dibromo-7-chloro-benzimidazole.

37 2-(3',4l'-dlch1oropheny1)-5-trifluoromethyl-benzimid- 223-225 azo e.

38 l. 2-(3,5-h1s-trltluoromethyl-t henyl)-5-trlflu0ro-methyl- 224-226 benzimidazole.

EXAMPLE 39 4.0 of 2-(3',4-dichlorophenyl)-4,5,6,7- tetrachlorobenzimidazole, produced as described in example 4, are suspended in about l00 ml. of ethanol, and 10 ml. of a normal aqueous potassium hydroxide solution are added thereto. The resulting clear solution is evaporated to dryness in vacuo, and the potassium salt of the aforesaid benzimidazole derivative is obtained as a white powder in almost quantitative yield.

In an analogous manner, but using normal aqueous sodium hydroxide solution in lieu of potassium hydroxide solution, the corresponding sodium salt is obtained.

EXAMPLE 40 20.0 g. of the starting benzimidazole used in example 39 are suspended in about 250 ml. of ethanol and a suspension of about 1.0 g. of finely pulverized magnesium oxide in about 50 ml. of water is added thereto. The resulting solution is evaporated to dryness in vacuo, and the neutral magnesium salt of 2-(3,4-dichlorophenyl)-4,5,6,7-tetrachlorobenzimidazole is obtained as a white powder in almost quantitative yield.

The new active substances of general formula l can be applied by the usual processes for textile finishing. They have considerable affinity to keratin material and are thus excellently suitable for the protection thereof from insects which eat it, particularly for the washproof mothproofing of such materials in the raw as well as in the process state, e.g., raw or processed sheeps wool as well as other animal hair, fells, feathers and furs. Compared with other active substances of the benzimidazole series, the new active substances of general formula I are distinguished by their good stability to washing.

In addition to their insecticidal activity against the larvae of the clothes moth, the compounds of formula I also have such an action against the larvae of the fur and carpet beetles so that textiles such as blankets, woollen carpets, woollen underwear, woollen outer clothes and knitted goods treated in any way desired with agents containing the new active substances are given lasting protection against all types of insects which injure keratin fibers by eating.

The testing of benzimidazoles of general formula I according to the as to their insecticidal action against such insects which eat keratin fibers and the testing of keratin textile materials treated with these active substances as to their resistance to attack from such pests were were in the following way; way: TEST METHODS and results AND RESULTS A 0.5 percent stock solution of the active substance to be tested in 2-r'nethoxyethanol is prepared. Then at room temperature, an aqueous application liquor is produced which, in 400 ml., contains 20 ml. of the said stock solution (0.1 g. active substance). l0 g. of wool flannel are then well wetted with hot water and introduced at room temperature. While constantly circulating the wool sample, the bath temperature is raised at 60 within 15 minutes, then 2 percent of formic acid calculated on the weight of the wool, are added and the sample is treated for another 30 minutes at this temperature in this liquor. It is then cooled, the wool sample is rinsed in running tapwater, centrifuged and hung up to dry. The concentration of active substance is 1 percent calculated on the weight of the wool.

The sample so dried is then subjected to a mothproofing test against clothes moths (Tineola biselliella) according to the prescription of the schweiz. Normenverbandes SNV 9590l (Swiss Association for Standardization, SNV 95901), and the fastness is tested against larvae of the fur beetle (Attagnus piceus) and the carpet beetle (Anthrenus vorax) according to SNV 95902; obviously, the method for Anthrenus larvae was applied to Attagenus piceus larvae by using 6-7 week old larvae of the latter type for the test. The method consists in cutting four pieces of equal size from the treated wool flannel sample and exposing each of these pieces for l4 days at a constant temperature (28 C.) and constant relative humidity (65percent) to attack (by eating) of 15 larvae of the corresponding pest (in each case two pieces exposed to the same pest.)

The results are given in the following table.

The evaluation is based on the loss in weight of the flannel sample and is shown in the table as follows:

xxxx very good action xxx good action xx moderate action x bad action.

TABLE II [1% active substance calculated on the weight of the Wool] Active substance Moths Attagenus Anthrenus '2-(4'-chlor0phenyl)4,5,6,7-tetrachlorobenzimldazole xxx xxx xxxx 2-(4-trifluoromethyl-phenyl)-4,5,6,7-

tetrachloro-benzlrntdazole xxxx xxxx xxx): 243',4-dichlorophenyl)-4,6,6,7-tetrachloro-benzimidazole xxxx xxxx xxxx 2-(3,4'-dlchlorophenyl)-4,5,6,7-tetrabrorno-benzlmldazole xxxx xxx xxxx 2-(3,6'-bis-trlfluoromethyl-phenyl)- 4,6,6,7-tetrachloro-benzimldazole xxxx xxxx xxxx 2-(3',6'-bis-trlfluoromethyl-phenyD- 4,5,6,7-tetrabromo-benzimidazole. xxxx xxxx xxxx z(3',4,6-trlchlorophenyl)-4,5,6,7-

tetrachloro-benzlmldazole xxxx xxxx xxxx 2-(4-chlorophenyl)-4,5,6-tri-chl0ro-7- broruo-benzimidazole xxxx xxxx xxxx 2-(3,4-dichlorophenyl)-4,5,6-trlchloro-7-bromobenzimldazole xxxx xxx xxx 2-(3,4'-dichlorophenyl)-6-br0mo- 4.5,7-trichlore-benzimidazole xxxx xxxx xxxx 2-(3,4-dlchlorophenyl)-4,6,7-tr1- chloro-benzimidazole xxxx xxxx xxxx 2-(3-trifluoromethyl-f-chlorophenyl)4,6,7-trlchloro-benzimidazole. xxxx xxxx xxxx 2-(3,4'-dlchlorophenyl)-4,6,7-trlmethyl-4,6-dibromo-7-ehlor0-benzimldazole xxxx xxxx xxxx 2-(3',4-dlchloropheny1)-4,7-dibromo- 5,6-d1chlow-benzimidazole xxxx xxxx xxxx 2-(3,4-d1chlorophenyl)-6-trifluoromethyl-benzimidazole xxxx xxxx xxxx Insecticidal and acaricidal agents according to the invention which contain the new active substances and can be used in, e.g., plant protection, can be in solid or liquid form, e.g., dusts, sprinkling agents or aqueous dispersions which are obtained from wettable powders, pastes or emulsion concentrates, and solutions and aerosols.

For the protection of keratin material from insects which eat it, the agents according to the invention should contain the new active substances in a finely distributed form. Thus, solutions, aqueous suspensions and emulsions are used in particular for this application.

The active substance of general formula I in the form of their alkali metal salts they generally have good water solubility. They can be brought onto keratin material direct from these aqueous solutions by dipping such material for a shorter or longer time in solutions of the alkali metal salts, or spraying it with the solutions or treating it therein at a raised temperature.

The keratin-protecting agents according to the invention can contain other known active substances in addition to the new active substances of general formula I. They can be combined, e.g., with halogenated anthranilic acid anilides, with halogenated and/or trifluoromethyl-substituted diphenyl ureas, with halogenated and sulfonated pheoxdiphenyl ureas and with 2-chloromethyl-sulphonylamino polychlorodiphenyl ethers.

The agents according to the invention are produced in the known way by intimately mixing the active substances with solid or liquid carriers and distributing agents. For the protection of keratin material, particularly organic solvents have proved valuable such as: propylene glycol, methoxyethanol, ethoxyethanol and dimethyl formamide. As distributing agents, emulsifying agents, e.g., sulfated caster oil, sulfite waste liquor and fatty alcohol sulfates can be used.

Keratinous materials can be impregnated with the active substances by the most varied textile finishing processes such as hot or cold, aqueous dye, chroming, pad dyeing or after treatment baths. The new active substances are fixed onto the keratin fiber not only by hot application but also by cold application.

Because of the good solubility in organic solvents, the active substances are also well suitable for application from nonaqueous media. Here, the materials to be protected can simply be impregnated with the solutions. With a suitable choice of solvent, the materials can be given an insecticidal finish also in a dry cleaning process.

The production and composition of agents according to the invention and their application for the protection of keratin materials from pests which eat it, are further illustrated in the following examples. Parts and percentages are given therein by weight and the temperatures are in degrees Centigrade.

EXAMPLE I 0.5 parts of 2(3,4'-dichlorophenyl)-4,5,6,7-tctrachlorobenzimidazole in the form of the sodium salt are dissolved with the aid of 10 parts of0. IN sodium hydroxide solution and a little ethanol. This solution is diluted with 3,000 parts of water and parts of wool are treated for 15 minutes in this liquor at 60. 5 parts of 10 percent acetic acid are then added and the treatment is continued at 60 for another hour. The wool is ten rinsed in the usual way and dried. On testing, it proves to be resistent to attack by moth larvae, fur and carpet beetle larvae.

EXAMPLE [I First, a 20 percent solution of 2-(4'-chlorophenyl)-4,5,6- trichloro-7-bromo-benzimidazole in Z-methoxyethanol is produced. 10 parts by volume of this solution are diluted with 200 parts by volume ofa solvent suitable for dry cleaning, e.g., a suitable benzine fraction (Diluan S). If desired, cleansing additives can be added. In addition, the compounds can also be used in the form of the alkali metal salts or can be converted into such in the solution by the addition of a slight amount of alkali liquor. The wool articles are treated in the usual way in this cleaning liquor and then centrifuged to a solvent content of about 100 percent of the weight of the wool. After drying, they prove to be mothproofed.

The same bath or those of analogous composition can be used in an analogous way for the mothproofing of untreated keratin-containing articles or of those which have been treated in some way or cleaned.

Similar mixtures can also be used for the sprinkling or spraying of wool in any stage of processing.

We claim:

1. A compound of the class consisting of 2-phenylbenzimidazoles of the formula wherein R is hydrogen or an alkali or alkaline earth metal cation, each X is fluorine, chlorine, bromine or trifluoromethyl,

and two of X are chlorine, bromine or trifluoromethyl, and the other X, is hydrogen, chlorine, bromine or trifluoromethyl, with the proviso that X and X, each may not represent more than two trifluoromethyl groups.

2. A compound as defined in claim 1, wherein said benzimidazole is 2-(3,4-dichlorophenyl)-4,5,6,7- tetrachloro-benzimidazoie.

3. A compound as defined in claim 1, wherein said benzimidazole is 2-(3',5-bis-trifiuoromethyl-phenyl)- 4,5,6,7tetrachloro-benzimidazole.

4. A compound as defined in claim 1, wherein said benzimidazole is 2-(3,5'-bis-trifluoromethyl-phenyl)-4,5,6,7- tetrabromo-benzimidazole.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3!624rl00 Dated NOV. 30, 1971 Wilhelm E. Frick, Horst Harle, Thomas Wenger, Inventor(s) i p I H It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 10, line 2: "a-(3',4'-dichlorophenyl) should be 2-(3' ,4 '-dichlorophenyl) Signed and sealed this 30th day of May 1972.

(SEAL) Attest:

EDWARD M.F'LETCHER, JR. ROBERT GOT'ISCHALK Attesting Officer Commissioner of Patents po'wso uscoMM-oc scan-Pu i IJS. GOVIIIUIIIIT PRINTING O'ICl "II O-lll-"l 

2. A compound as defined in claim 1, wherein said benzimidazole is 2-(3'',4''-dichlorophenyl)-4,5,6,7-tetrachloro-benzimidazole.
 3. A compound as defined in claim 1, wherein said benzimidazole is 2-(3'',5''-bis-trifluoromethyl-phenyl)-4,5,6,7tetrachloro-benzimidazole.
 4. A compound as defined in claim 1, wherein said benzimidazole is 2-(3'',5''-bis-trifluoromethyl-phenyl)-4,5,6,7-tetrabromo-benzimidazole.
 5. A compound as defined in claim 1, wherein said benzimidazole is 2-(3'',4''-dichlorophenyl)-4,6-dibromo-5-trifluoromethyl-7-chloro -benzimidazole.
 6. A compound as defined in claim 1, wherein said benzimidazole is 2-(3'',5''-bis-trifluoromethyl-phenyl)-4,6-dibromo-5-trifluoromethyl-7-chloro -benzimidazole. 